CN107675283B - High-strength aromatic copolyamide fiber and preparation method thereof - Google Patents
High-strength aromatic copolyamide fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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Abstract
The invention discloses a high-strength aromatic copolyamide fiber, which is prepared by introducing a nitrile group and a heterocyclic unit into a high-molecular main chain in a low-temperature polycondensation mode from the research of molecular design and screening structures, and is characterized in that: the fiber is prepared by polymerization of 2, 5-diaminobenzonitrile (CyPPD), 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI), p-phenylenediamine (PPD) and terephthaloyl chloride (TPC) in a solvent system according to a molar ratio to prepare spinning slurry, filtration, defoaming, dry-jet wet spinning, multi-stage stretching, washing, drying, heat treatment, oiling, drying and winding, and the specific indexes of the fiber comprise: the fiber has the tensile strength of 3.5-5.5 Gpa, the initial modulus of 110-165 Gpa, the elongation at break of 2.5-4.5 percent, the single fiber fineness of 1.2-2 dtex and the bundle yarn fineness of 18-300 tex. The invention greatly improves the production efficiency and protects the environment, reduces the industrialization cost and keeps the production cost at a relatively low level.
Description
Technical Field
The invention belongs to the technical field of high molecular polymers, and particularly relates to a high-strength heterocyclic aromatic copolyamide fiber and a production method thereof.
Background
Wholly aromatic polyamide fibers, also known as aramid fibers, are polyamides of long-chain structures in which at least 85% of amide groups (CONH) and two aromatic rings are connected on the molecular main chain, which are produced by the reaction of aromatic diamines and aromatic dicarboxylic acid dihalides. The aramid fibers are known to have more types and have very large difference in structural performance, and can be divided into meta-aramid fibers and para-aramid fibers according to structures, wherein the representative meta-aramid fibers mainly comprise poly (m-phenylene diamide-m-phenylenediamine) (meta-aramid fibers and MPIA), have high temperature resistance, but have relatively low strength modulus; para-aramid fibers have high strength, high modulus, and high temperature resistance, and are commercially available in many types, such as Kevlar (para-aramid, PPTA) from dupont, heterocyclic aramid (Armos) from russian camersk chemical fiber, and Technora (Technora) from japan. Kevlar is prepared by using p-phenylenediamine (PPD) and terephthaloyl chloride (TPC) as main raw materials through polycondensation reaction and spinning process, and related technologies are patents US3,673,143 and US4,308,374; technora is a compound component required by para-aramid, and a third monomer 3,4 '-diaminodiphenyl ether (3, 4' -ODA) is introduced to be prepared through polycondensation and spinning processes, and related technologies are patents US3,637,162, US4,342,715 and the like; the aromatic polyamide is also prepared by introducing a third monomer 2- (4-aminophenyl) -5 (6) -aminobenzimidazole (DAPBI) on the basis of a compound component required by para-aramid and performing polycondensation reaction and spinning processes, and related technologies are RU2017866, US5,233,004 and the like.
The heterocyclic aramid fiber is one of important varieties in aromatic polyamide fiber series, and is representatively introduced with a third monomer of 2- (4-aminophenyl) -5 (6) -aminobenzimidazole ternary polymerization heterocyclic aramid fiber (aramid fiber III), and the heterocyclic aramid fiber has more excellent mechanical properties of strength, toughness and impact resistance than para-aramid fiber (aramid fiber II). The introduction of the benzimidazole structure reduces the regularity and intermolecular force of polymer molecular structure chains, so that the three-dimensional crystal structure is reduced, the polymer molecules obtain the maximum orientation along the axial direction in the spinning and drawing process, and the crystal structure is perfected in the high-temperature and heat treatment process, so that the tensile strength and the modulus are greatly improved. The comparative test results show that the breaking strength and the elastic modulus of the heterocyclic aramid armor are respectively higher than that of kevlar49 by more than 30% and 20%. The heterocyclic aramid fiber has more excellent comprehensive performance, occupies irreplaceable important position in high-performance fiber, and is widely applied to the fields of aerospace, national defense and military industry, civil advanced material application and the like. The prior patent publications CN101781400A and CN101781813A disclose a fluorine-containing polyaramide fiber and a preparation method thereof, the patent CN104357939A discloses a chlorine-containing high-performance heterocyclic aramid fiber and a preparation method thereof, the patent CN101857979 discloses an aramid fiber containing a pyrimidine structure and a preparation method thereof, and the patent CN102383218A and the patent KR10-2017-0017831 disclose a polyaramide fiber containing a nitrile group structure and a preparation method thereof. The above-mentioned patent discloses that on the basis of the original compound component formed from para-aramid fiber, a novel third monomer compound is introduced, and the molecular structure of aromatic amide polymer is changed by copolymerization, so that the original excellent characteristics of para-aramid fiber are greatly retained, and the heterocyclic aromatic amide fiber with competitive advantages in terms of mechanical property and cost performance of aromatic amide fiber is further improved, and becomes an important new trend in the future of development of aramid fiber.
Disclosure of Invention
The invention aims to solve the technical problem of introducing nitrile-containing groups and heterocyclic units on a high-molecular main chain in a low-temperature polycondensation mode from the research of molecular design and screening structures, thereby providing a high-strength aromatic copolyamide fiber and a complete production method from polymerization to spinning. The purpose of the invention is realized by the following technical scheme:
a high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber has the tensile strength of 3.5-5.5 Gpa, the initial modulus of 110-165 Gpa, the elongation at break of 2.5-4.5%, the single-filament fineness of 1.2-2 dtex, the bundle yarn fineness of 18-300 tex, and the molecular structural formula is as follows:
wherein the mole number of the terephthaloyl chloride (TPC) is equal to 0.995-1.005 of the sum of the mole numbers of the 2, 5-diaminobenzonitrile (CyPPD), the 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) and the p-phenylenediamine (PPD), the mole ratio is m + n + i =1, 0< m <1, 0< n < 0.75, 0< i < 0.25, and the solid content of the polymer in the spinning stock solution is 3-7 wt%.
The preparation method of the high-strength heterocyclic aromatic copolyamide fiber containing the nitrile group comprises the following process steps:
(1) polymerization of nitrile-containing heterocyclic copolyamide and preparation of spinning slurry: adding 2, 5-diaminobenzonitrile, 2- (4-aminophenyl) -5-aminobenzimidazole and p-phenylenediamine into a solvent system, uniformly stirring under the protection of nitrogen until the mixture is completely dissolved, and then, heating in a reaction kettleCooling to-10-5 deg.C, adding terephthaloyl chloride 2-3 times, stirring for 1-3 hr, and polymerizing to obtain homogeneous spinning solution with intrinsic viscosity of 6.5-9.0 d L/g and dynamic viscosity of 6-20 ten thousand centipoise, wherein the solvent system is one or combination of dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Dimethylformamide (DMF), and the chloride salt is calcium chloride (CaCl)2) Lithium chloride (L iCl), the amount of chloride salt is 2-6 wt% of the weight of the solvent, and the moisture content of the solvent system is 30-70 ppm;
(2) dry-jet-wet spinning: homogenizing, filtering and defoaming the polymerized spinning slurry, and performing dry-jet wet-process spinning by adopting a coagulation bath to obtain nascent fiber, wherein the spinning speed is 50-150 m/min, in the dry-jet wet-process spinning, the temperature of a spinning solution is 20-45 ℃, the height of an air layer is 5-20 mm, and unstable spinning and doubling conditions are easy to occur in other ranges; the bath liquid of the coagulating bath is a mixed liquid of an organic solvent and water, the organic solvent is any one or a combination of dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP), and the content of the organic solvent is 20-30%; the spinneret plate for spinning is hollow and round, the inner diameter is 10-25 mm, the outer diameter is 45-60 mm, the number of holes is 150 and 1500, and the hole diameter is 0.06-0.1 mm;
(3) multi-stage stretching: the nascent fiber is subjected to multi-stage drafting in a plasticizing bath to enable the total stretching rate to reach 50% -150%, and the plasticizing liquid is a 5-20% dimethylacetamide (DMAc) water solution or an N-methylpyrrolidone (NMP) water solution;
(4) washing: first-stage water washing to remove solvent and by-product; grade 2 0.1-3% NaOH or Ca (OH)2Washing with weak alkali liquor to remove acidic byproducts; third-stage water washing to further remove impurities; washing temperature: 10-60 ℃;
(5) and (3) heat treatment: firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section and is treated for 0.5 to 2 minutes at 180 to 300 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 0.5-2 minutes at 380-500 ℃ in a nitrogen atmosphere;
(6) winding: oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber, wherein the drying is contact roller drying and the temperature is 90-160 ℃.
The chemical reaction formula for preparing the nitrile group-containing heterocyclic aramid fiber is as follows:
the beneficial technical effects brought by the invention are as follows:
the invention provides a high-strength heterocyclic aromatic copolyamide fiber and a complete set of production method from polymerization to dry-jet-wet continuous stable high-efficiency spinning, which is based on molecular design and screening structure research and aims to introduce a nitrile group and a heterocyclic unit into a high-molecular main chain in a low-temperature polycondensation mode, and has a complete process system.
The introduction of structures containing nitrile aniline and benzimidazole reduces the regularity and intermolecular force of polymer molecular structure chains, so that the three-dimensional crystal structure is reduced, the polymer molecules obtain the maximum orientation along the axial direction in the spinning and stretching process, the crystal structure is perfected in the high-temperature heat treatment process, so that the tensile strength and the modulus are greatly improved, the fiber tensile strength is 3.5-5.5 Gpa, the initial modulus is 110-165 Gpa, and the elongation at break is 2.5-4.0%. The material is widely applied to the fields of aerospace, national defense, military industry, civil tip material application and the like, and fills the market gap.
The method greatly simplifies the fiber preparation process, and reduces the industrial cost and keeps the production cost at a relatively low level due to mature technology, easy control, environmental protection and high production efficiency. The invention has perfect process system, can obviously improve the mechanical property of the fiber and simultaneously improve the composite property of the fiber.
Detailed Description
The present invention is further described in detail by the following examples, which should be construed as being limited only by the scope of the invention as defined in the claims, and not by the essential modifications and adaptations of the invention as described above.
Example 1, a process for the production of high strength heterocyclic aromatic copolyamide fibers, carried out according to the following steps:
1. preparation of a polymerization spinning slurry:
in a reaction kettle in a nitrogen environment, according to the molar ratio of TPC to CyPPD to DAPBI =10:3.3:6.7, 0.676kg of high-purity (more than 99.9%) 2, 5-diaminobenzonitrile (CyPPD) and 2.313kg of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) diamine monomers are added into a solvent system of 100 liters (L) dimethylacetamide (DMAc) and 3.748kg of lithium chloride (L iCl), then the system is cooled to-5 ℃ after being stirred to completely dissolve the CyPPD and the DAPBI, 3.125kg of terephthaloyl chloride (TPC) is added into the system and fully stirred for 3 hours to obtain a polymer homogeneous spinning solution with the intrinsic viscosity of 7.5d L/g and the dynamic viscosity of 11 ten thousand centipoise;
wherein, TPC is added for 3 times, the solid content of the polymer in the spinning slurry is 5wt%, the content of the DMAc/L iCl solvent system is 4wt%, and the water content is 50ppm, wherein the total amount of TPC is 40% of the first time, 30% of the second time and 30% of the third time;
2. spinning:
filtering and defoaming the spinning slurry (less than or equal to 5 microns), and performing dry-jet wet spinning, wherein the number of spinneret holes is 667, the aperture is 0.07mm, the length-diameter ratio is 0.5, the spinning stock solution passes through an air layer of 8mm and enters a coagulation bath at the temperature of 0-5 ℃, and the spinning speed is 80m/min, wherein the coagulation solution is 20% dimethylacetamide aqueous solution;
3. stretching: 2-stage drafting the nascent fiber in a plasticizing bath of 10% dimethyl acetamide water solution to reach a stretching ratio of 120%; washing, namely washing with water at the first stage to remove the solvent and byproducts; grade 2 0.5% NaOH or Ca (OH)2Washing with weak base to remove acidic by-products; third-stage water washing to further remove impurities; washing temperature: 10-60 ℃; drying;
4. thermal treatment
Firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section and is treated for 30sec at 200 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 20sec at 380 ℃ in a nitrogen atmosphere; and further oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber. The drying is contact roller drying, and the temperature is 120 ℃.
The high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is prepared by taking a polymer with the intrinsic viscosity of 7.5d L/g as a starting point, the intrinsic viscosity of the fiber is reduced by less than 0.2d L/g compared with the intrinsic viscosity of the polymer, the dynamic viscosity of the fiber is 11 ten thousand centipoise, and the specific indexes of the fiber comprise tensile strength of 4.96Gpa, initial modulus of 165.2Gpa, elongation at break of 3.5%, single fiber fineness of 1.5dtex and bundle yarn fineness of 100 tex.
Example 2, a method for producing a high-strength heterocyclic aromatic copolyamide fiber, comprising the steps of:
1. polymerization of spinning dope:
in a reaction kettle in a nitrogen environment, according to the molar ratio of TPC to CyPPD to DAPBI to PPD =10:1.7:6.6:1.7, adding 0.207kg of high-purity (more than 99.9%) 2, 5-diaminobenzonitrile (CyPPD), 1.354kg of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) and 0.168kg of p-phenylenediamine (PPD) into a solvent system of 100 liters (L) dimethylacetamide (DMAc) and 3.748kg of lithium chloride (L iCl) according to the molar ratio of TPC to CyPPD to DAPBI, stirring to completely dissolve the CyPPD and DAPBI, cooling the system to-10 ℃, adding 1.857kg of terephthaloyl chloride (TPC) into the system, and fully stirring for 3 hours to obtain a polymer spinning stock solution with the intrinsic viscosity of 7.2d L/g and the dynamic viscosity of 9 ten thousand;
wherein, TPC is added for 3 times, 40 percent of the total amount of the first addition, 30 percent of the total amount of the second addition and 30 percent of the total amount of the third addition, the solid content of the polymer in the spinning slurry is 3 weight percent, the content of the DMAc/L iCl solvent system is 3.5 weight percent, and the water content is 50 ppm;
2. spinning:
filtering and defoaming the spinning slurry (less than or equal to 5um), and performing dry-jet wet spinning, wherein the number of spinneret holes of a spinneret plate is 200, the hole diameter is 0.63mm, the length-diameter ratio is 1.5, the spinning stock solution passes through a 10mm air layer and enters a solidification bath with 30% dimethylacetamide aqueous solution as a solidification solution at the temperature of 0-5 ℃, and the spinning speed is 80m/min;
3. stretching: 2-stage drafting of the nascent fiber in a plasticizing bath of 20% dimethyl acetamide water solution to reach a stretching ratio of 100%; washing, namely washing with water at the first stage to remove the solvent and byproducts; grade 2 3% NaOH or Ca (OH)2Washing with weak base to remove acidic by-products; third-stage water washing to further remove impurities; washing temperature: 10-60 ℃; drying;
4. thermal treatment
Firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section, and is treated for 20sec at 180 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 20sec at 400 ℃ in a nitrogen atmosphere; further oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber; the drying is contact roller drying, and the temperature is 100 ℃.
The high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is prepared by taking a polymer with the intrinsic viscosity of 7.2d L/g as a starting point, the intrinsic viscosity of the fiber is reduced by less than 0.2d L/g compared with the intrinsic viscosity of the polymer, the dynamic viscosity of the fiber is 9 ten thousand centipoise, and the specific indexes of the fiber comprise tensile strength of 4.7Gpa, initial modulus of 153.2Gpa, elongation at break of 3.8%, single fiber fineness of 1.47dtex and bundle yarn fineness of 29.4 tex.
Example 3, a method for producing high strength heterocyclic aromatic copolyamide fibers, comprising the steps of:
1. polymerization of spinning dope:
in a reaction kettle in a nitrogen environment, according to the molar ratio of TPC to CyPPD to DAPBI =10:5:5, 1.548kg of high-purity (more than 99.9%) 2, 5-diaminobenzonitrile (CyPPD) and 2.608kg of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) diamine monomers are added into a solvent system of 100 liters (L) of dimethylacetamide (DMAc) and 5.622kg of lithium chloride (L iCl) after stirring to completely dissolve the CyPPD and the DAPBI, the system is cooled to 0 ℃, 4.722kg of terephthaloyl chloride (TPC) is added into the system and fully stirred for 3 hours to obtain a polymer homogeneous spinning stock solution with the intrinsic viscosity of 6.8d L/g and the dynamic viscosity of 8 ten thousand centipoises;
wherein, TPC is added for 3 times, the solid content of the polymer in the spinning slurry is 7wt%, the content of the DMAc/L iCl solvent system is 6wt%, and the water content is 50ppm, wherein the TPC is 40% of the total amount of the first addition, 30% of the total amount of the second addition and 30% of the total amount of the third addition;
2. spinning:
filtering and defoaming the spinning slurry (less than or equal to 5um), and performing dry-jet wet spinning, wherein the number of spinneret holes is 400, the aperture is 0.08mm, the length-diameter ratio is 2.0, the spinning stock solution passes through a 10mm air layer and enters a 25% dimethylacetamide aqueous solution coagulating bath at the temperature of 0-5 ℃, and the spinning speed is 120 m/min;
3. stretching: the nascent fiber is subjected to 3-stage drafting in a plasticizing bath of 20% dimethylacetamide aqueous solution, and the stretching ratio reaches 120%; washing, namely washing with water at the first stage to remove the solvent and byproducts; grade 2 0.1% NaOH or Ca (OH)2Washing with weak base to remove acidic by-products; third-stage water washing to further remove impurities; washing temperature: 10-60 ℃; drying;
4. thermal treatment
Firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section, and is treated for 30sec at 220 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 20sec at 350 ℃ in a nitrogen atmosphere; and further oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber. The drying is contact roller drying, and the temperature is 120 ℃.
The high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is prepared by taking a polymer with the intrinsic viscosity of 6.8d L/g as a starting point, the intrinsic viscosity of the fiber is reduced by less than 0.2d L/g compared with the intrinsic viscosity of the polymer, the dynamic viscosity of the fiber is 8 ten thousand centipoise, and the specific indexes of the fiber comprise tensile strength of 4.5Gpa, initial modulus of 147.5Gpa, elongation at break of 3.2%, single fiber fineness of 2.0dtex, and bundle yarn fineness of 80 tex.
Example 4, a method for producing high strength heterocyclic aromatic copolyamide fibers, comprising the steps of:
1. polymerization of spinning dope:
in a reaction kettle in a nitrogen environment, according to the molar ratio of TPC (CyPPD): DAPBI: PPD =10:2.5:5:2.5, three diamine monomers of high purity (more than 99.9%) 2, 5-diaminobenzonitrile (CyPPD) 0.434kg, 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) 1.462kg and p-phenylenediamine (PPD)0.353kg are added into a solvent system of 100 liters (L) dimethylacetamide (DMAc) and 1.874kg of lithium chloride (L iCl), then stirring is carried out to completely dissolve CyPPD and DAPBI, the system is cooled to 5 ℃, 2.647kg of terephthaloyl chloride (TPC) is added into the system, and the mixture is fully stirred for 3 hours to obtain a polymer spinning dope with the intrinsic viscosity of 6.7d L/g and the dynamic viscosity of 8 ten thousand;
wherein, TPC is added for 2 times, 50 percent of the total amount of the first addition and 50 percent of the total amount of the second addition, the solid content of the polymer in the spinning slurry is 4 weight percent, the content of the DMAc/L iCl solvent system is 2 weight percent, and the water content is 50 ppm;
2. spinning:
filtering and defoaming (less than or equal to 5um) the spinning slurry, and carrying out dry-jet wet spinning, wherein the number of spinneret holes is 800, the aperture is 0.07mm, the length-diameter ratio is 2, the spinning stock solution passes through an air layer of 12mm and enters a solidification bath of 25% dimethylacetamide (DMAc) aqueous solution at the temperature of 0-5 ℃, and the spinning speed is 100m/min;
3. stretching: 2-stage drafting of the nascent fiber in a plasticizing bath to reach a stretching ratio of 110%; washing and drying;
4. thermal treatment
Firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section and is treated for 30sec at 200 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 20sec at 400 ℃ in a nitrogen atmosphere; and further oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber. The drying is contact roller drying, and the temperature is 90-160 ℃.
The high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is prepared by taking a polymer with the intrinsic viscosity of 6.7d L/g as a starting point, the intrinsic viscosity of the fiber is reduced by less than 0.2d L/g compared with the intrinsic viscosity of the polymer, the dynamic viscosity of the fiber is 8.1 ten thousand centipoise, and the specific indexes of the fiber comprise tensile strength of 4.1Gpa, initial modulus of 140Gpa, elongation at break of 3.1%, single fiber fineness of 1.5dtex and bundle yarn fineness of 120 tex.
Example 5, a method for producing high strength heterocyclic aromatic copolyamide fibers, comprising the steps of:
1. polymerization of spinning dope:
in a reaction kettle in a nitrogen environment, according to the molar ratio of TPC to CyPPD to DAPBI =10:3.3:6.7, two diamine monomers of 0.586kg of high-purity (more than 99.9%) 2, 5-diaminobenzonitrile (CyPPD) and 2.004kg of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) are added into a solvent system of 100 liters (L) of N-methylpyrrolidone (NMP) and 3.589kg of lithium chloride (L iCl) and then stirred to completely dissolve the CyPPD and the DAPBI, the system is cooled to-5 ℃, 2.706kg of terephthaloyl chloride (TPC) is added into the system and fully stirred for 3 hours to obtain a homogeneous polymer spinning stock solution with the intrinsic viscosity of 7.2d L/g and the dynamic viscosity of 9.6 ten thousand centipoise;
wherein, TPC is added for 3 times, 40 percent of the total amount of the first addition, 30 percent of the total amount of the second addition and 30 percent of the total amount of the third addition, the solid content of the polymer in the spinning slurry is 4 weight percent, the content of the DMAc/L iCl solvent system is 3.5 weight percent, and the water content is 50 ppm;
2. spinning:
filtering and defoaming the spinning slurry (less than or equal to 5 microns), and performing dry-jet wet spinning, wherein the number of spinneret holes is 667, the aperture is 0.07mm, the length-diameter ratio is 0.5, the spinning stock solution passes through an air layer of 8mm and enters a coagulation bath of 20 percent N-methylpyrrolidone aqueous solution at the temperature of 0-5 ℃, and the spinning speed is 80m/min;
3. stretching: 2-stage drafting of the nascent fiber in a plasticizing bath to reach a stretching rate of 120%; washing and drying;
4. thermal treatment
Firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section and is treated for 30sec at 200 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 20sec at 420 ℃ in a nitrogen atmosphere; and further oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber. The drying is contact roller drying, and the temperature is 90-160 ℃.
The high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is prepared by taking a polymer with the intrinsic viscosity of 7.2d L/g as a starting point, the intrinsic viscosity of the high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is reduced by less than 0.2d L/g compared with the intrinsic viscosity of the polymer, the dynamic viscosity of the high-strength nitrile group-containing heterocyclic aromatic copolyamide fiber is 9.6 ten thousand centipoise, and the specific indexes of the fiber comprise tensile strength of 4.8Gpa, initial modulus of 160.5Gpa, elongation at break of 3.6%, single-filament fineness of 1.5dtex and bundle yarn fineness of 100 tex.
Claims (2)
1. A high-strength aromatic copolyamide fiber has the tensile strength of 3.5-5.5 Gpa, the initial modulus of 110-165 Gpa, the elongation at break of 2.5-4.5%, the single-fiber fineness of 1.2-2 dtex, the bundle yarn fineness of 18-300 tex, and the molecular structural formula is as follows:
in the formula, the molar ratio is m + n + i =1, 0< m <1, 0< n < 0.75, and 0< i < 0.25.
2. A method for preparing a high strength aromatic copolyamide fiber according to claim 1, characterized in that: is carried out according to the following steps
(1) Adding 2, 5-diaminobenzonitrile (CyPPD), 2- (4-aminophenyl) -5-aminobenzimidazole and (DAPBI) and p-phenylenediamine (PPD) into a solvent system, uniformly stirring under the protection of nitrogen until the mixture is completely dissolved, then reducing the temperature in a reaction kettle to-10-5 ℃, adding terephthaloyl chloride (TPC) for 2-3 times, fully stirring for 1-3 hours, and obtaining a homogeneous spinning stock solution after the polymerization reaction is terminated, wherein the intrinsic viscosity of the obtained polymer is 6.5-9.0 d L/g, and the dynamic viscosity is 6-20 ten thousand centipoise;
the mole number of the paraphthaloyl chloride is equal to 99.5-100.5% of the neutralization of the mole numbers of the 2, 5-diaminobenzonitrile, the 2- (4-aminophenyl) -5-aminobenzimidazole and the p-phenylenediamine, and the solid content of the polymer of the spinning solution is 3-7 wt%;
the solvent system is one or combination of dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP), and the chlorine salt is calcium chloride (CaCl)2) Chlorine (C)Any one or the combination of lithium chloride (L iCl), the dosage of chloride salt is 2-6 wt% of the weight of the used solvent, and the moisture content of the solvent system is 30 ppm-70 ppm;
(2) dry-jet-wet spinning: homogenizing the polymerization spinning solution, filtering, defoaming, adopting dry-jet-wet spinning, and coagulating in a coagulating bath to obtain nascent fiber, wherein the spinning speed is 50-150 m/min;
(3) multi-stage stretching: 2-3 levels of drafting are carried out on the nascent fiber in a plasticizing bath, and the total stretching ratio reaches 50% -150%;
(4) washing: first-stage water washing to remove solvent and by-product; 2, performing alkaline washing to remove acidic byproducts; third-stage water washing to further remove impurities; washing temperature: 10-60 ℃;
(5) and (3) heat treatment: firstly, the nascent fiber enters a preheating and stretching treatment section from a spinning drying section and is treated for 0.5 to 2 minutes at 180 to 300 ℃ in a nitrogen atmosphere; secondly, entering a thermal crystallization treatment section, and treating for 0.5-2 minutes at 380-500 ℃ in a nitrogen atmosphere;
(6) winding: oiling, drying and winding the tows to obtain the nitrile group-containing heterocyclic aromatic copolyamide fiber.
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| CN113668091B (en) * | 2020-05-13 | 2023-02-10 | 中蓝晨光化工研究设计院有限公司 | High-strength high-elongation heterocyclic aromatic polyamide fiber and preparation process thereof |
| CN114606598B (en) * | 2022-04-18 | 2023-11-07 | 江苏新视界先进功能纤维创新中心有限公司 | Heterocyclic meta-aramid fiber and preparation method thereof |
| CN114959926B (en) * | 2022-04-29 | 2023-11-28 | 上海华峰超纤科技股份有限公司 | Drawing process of PET (polyethylene terephthalate) nascent fiber |
| CN117418325A (en) * | 2023-11-29 | 2024-01-19 | 四川辉腾科技股份有限公司 | High-elongation heterocyclic aramid fiber and preparation method thereof |
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| CN101921395A (en) * | 2010-02-10 | 2010-12-22 | 中蓝晨光化工研究院有限公司 | High-performance heterocyclic aramid fiber as well as preparation and application thereof |
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